FR2960237A1 - ORGANIC COMPOUNDS, PROCESS FOR PREPARATION AND USES IN ELECTRONICS - Google Patents

Abstract

The present invention relates to novel organic compounds, to their methods of preparation and to their uses, firstly in the field of electronics, particularly in the fields of plastic electronics and molecular electronics and of on the other hand in the field of coatings, in particular in the fields of adhesion primers and intelligent coatings. The invention also relates to a material comprising a novel compound according to the invention.

Description

ORGANIC COMPOUNDS, PROCESS FOR PREPARATION AND USES IN ELECTRONICS

DESCRIPTION TECHNICAL FIELD The present invention relates to novel organic compounds, to their processes of preparation and to their uses, firstly in the field of electronics, particularly in the fields of plastic electronics and plastics. molecular electronics and secondly in the field of coatings, particularly in the fields of adhesion primers and intelligent coatings. The invention also relates to a material comprising a novel compound according to the invention. In the description below, references in brackets [] refer to the list of references at the end of the text. STATE OF THE ART For several years, research aimed at developing new organic compounds, in the form of a crystal or a polymer, for example, which show properties similar to inorganic compounds, continues to grow. These properties are conduction by electrons and holes, as well as the presence of a band gap. In addition, research to develop new functional coatings is also very active. Due to their elasticity, lightness, strength and plasticity, organic molecules are of great interest, particularly because of the extent of their fields of application in electronics or as functional coatings. In contrast to materials based on inorganic compounds (inorganic materials) such as silicon for example, the materials based on organic molecules (organic materials) have the advantage of being deposited and / or grafted, in the form of thin films or thin films by inexpensive techniques, on flexible substrates and light, conductive or insulating.

In addition, as inorganic materials, organic materials can be doped, that is to say the electron density (N-doping) or holes (P-doping), can be increased. The immobilization of organic compounds, in the form of a polymer, for example, on insulating substrates, metal, semiconductor or carbon-based, makes it possible to develop new interfaces for applications that can range from the manufacture of molecular electronic devices or plastics, bio-sensor systems, anticorrosion coatings, intelligent coatings. The formation of layers or thin films resulting from the grafting or deposition of organic molecules or polymers on the surface of the substrates, makes it possible both to maintain the properties of the substrates and to give the surface of the material new and distinct properties. . One particularly interesting property is the ability to switch between different states of electrical conduction. The nature of the organic compounds can determine the electrical potential at which the layer switches. To date, the existing organic compounds capable of forming layers deposited or grafted onto the surface of the substrates do not give full satisfaction for at least one of the following reasons: they are not suitable for any type of substrates in the in which direction they may not form layers or thin films by grafting or depositing on any type of substrate; the layer or layers formed are not always homogeneous (in particular in thickness), which may affect the quality and the properties of the layer and of the substrate on which it is deposited or grafted; interface between the substrate and the layer (s) and thus the quality of the material or devices using these layers; the number of deposited or grafted layers can not be modulated, which can lead to films that are either too thin or too thick, and thus affect the quality and the properties of this layer, of the substrate on which said layer is deposited or grafted, the interface and therefore the quality of the material or devices using these layers; the nature of the interface between the substrate and the layer is not always controlled, which can lead to weakly adhering layers and / or to an interface having inadequate injection or hole-hole barriers for intended uses, and may affect the quality of devices using these layers; the layer or layers formed often have defects of micron or subnanometric size which adversely affect the quality of the layer, the substrate on which it is deposited or grafted, the interface and consequently the quality of the material or devices using these layers ; Although grafted onto the substrate, the layer or layers formed are not always electroactive, which may lead to properties that can not be adjusted via an electrochemical or electrical stimulus (injection of electrons or holes, for example). and thus affect the quality of devices using these layers; Although grafted onto the substrate, the electroactive layer or layers formed do not always switch between two states having different conduction properties; the electroactive layer or layers formed do not always switch between two states having different conduction properties at the desired electrical or electrochemical potential, which can affect the quality of the devices using these layers; the use of organic compounds and / or the formation of organic polymers can pose technical problems, particularly in terms of reproducibility and / or industrialization. The need for new organic compounds capable of forming one or more electroactive layers that can switch between an insulating state and a conductive state on the surface of different types of substrates, overcoming the defects, disadvantages and obstacles of the state of the art , remains relevant. There is therefore a real need for new organic compounds that are compatible with any type of substrate and capable of forming one or more layer (s) on their surface.

There is also a real need to propose new organic compounds whose implementation and / or polymer formation is easy and reproducible, industrially feasible and economically interesting. DESCRIPTION OF THE INVENTION The present invention is specifically intended to meet these needs by providing compounds of formula (I): ## STR2 ## wherein R 1 represents a hydrogen atom a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a -COOR3 group, a --COR3 group, a -SR3 group, a -SeR3 group, a -Si (OR3) group, a -NR3R4 group a -CEN group, a -N3 group, a -CEC-H group, a heterocycle selected from the group consisting of pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a polyethylene group of formula ± O-CH 2 -CH 2 49-, a C1-C10 alkyl group, a phenyl group, said polyethylene, alkyl, phenyl groups being optionally substituted by one or more groups selected from the group consisting of: - a group -COOR3, a group -COR3, a hydroxyl group, a C1-C4 alkoxy group, -CONR3R4, -NR3R4; R2 is phenyl, -NH2, aniline, meta-toluidine, anisidine, metatrifluoromethylaniline, paraphenylenediamine (PPD), amino-4-diphenyl, optionally substituted with one or more groups selected from C1-C4 alkyl, -COOR3, -COR3, hydroxyl, C1-C4 alkoxy, -CONR3R4, diazo (N2 +), group -NO2, a group -NR3R4; X, Y and Q represent, independently of each other, O, Se, S, Te, NR 3, P (O), P (R 3); Z represents a heterocycle selected from the group consisting of pyrrole, furan, thiophene, selenophene, phosphole, said heterocycle being optionally substituted with one or more groups selected from the group consisting of: - a C1-C10 alkyl group a carboxyl group, a group - COOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; N = 1,2,3,4,5; m = 0,1,2,3; ρ = 0.1,2,3,4,5; q = 0.1; ## STR5 ## A and B represent, independently of one another, a C 1 -C 10 alkyl group; or q = 0, A represents a -CH 2 - group and forms a direct bond with Y to give a 5-membered heterocycle; or q = 1, A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; or where q = 1, A and B together with X and Y to which they are attached form a 7-membered heterocycle, wherein A is -CH 2 - and B is -CH 2 -CH 2 -, or B is -CH2 group and A - CH2-CH2- group; It being understood that when q = 1, X = Y = O, Q = S, A and B together with X and Y to which they are attached form a 6-membered heterocycle in which A and B each represent - (CH 2) -, RI represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is different from 1. The compounds of formula (I), have the advantage of being compatible with any type of substrate and can form one or more layer (s) on their surface.

The formation of said layer (s) on the surface of the substrate may be by deposition or by grafting of the compounds of formula (I). For the purposes of the invention, deposition means the formation of one or more layers on the surface of a substrate by oxidation of the compounds of formula (I), and by grafting is meant the formation of one or more layers on the surface of a substrate by reduction of said compounds of formula (I). Thus, the compounds of formula (I) may adhere to the substrates by grafting. The grafting can be done by means of any type of bonds allowing a good adhesion of said compounds on the substrate, for example by means of strong bonds. For the purposes of the present invention, the term "alkyl" means a linear, branched or cyclic saturated carbon group, optionally substituted, comprising 1 to 10 carbon atoms, for example 1 to 6 carbon atoms, for example 1 to 4 carbon atoms. carbon atoms. As an indication, mention may be made of methyl, ethyl, propyl, iso-propyl, n-butyl, sec-butyl iso-butyl, tert-butyl, cyclobutyl, pentyl (or amyl), sec-pentyl, iso-pentyl groups. , neopentyl, hexyl, isohexyl, tert-hexyl, neohexyl, heptyl, octyl, nonyl, decyl and their branched and / or cyclic isomers. For the purposes of the present invention, the term "heterocycle" means a system comprising at least one aromatic ring, a saturated or unsaturated cycle comprising at least one heteroatom chosen from the group comprising sulfur, oxygen, nitrogen, phosphorus. In the context of the invention, the heterocycles may comprise from 3 to 20 carbon atoms. The heterocycles may be substituted. By way of example of a heterocycle, mention may be made of pyrrolidine, pyrazoline, pyrazolidine, imidazole, imidazolidine, piperidine, piperazine, oxazolidine, isoxazolidine, morpholine, thiazole, thiazolidine, isothiazolidine, tetrahydrofuran, pyridine, bipyridine, terpyridine, pyridazine, pyrazine, pyrimidine, pyrrole, pyrazole, triazole, imidazoline, thiazoline, oxazole, oxazoline , isooxazoline, thiadiazoline, oxadiazoline, thiophene, furan, quinoline, isoquinoline, benzopyrrole, benzofuran, benzothiophene. phosphole, tetrathiafulvalene, selenophene, phenanthroline, and the like. For the purposes of the present invention, the term "alkoxy" means a linear, branched or cyclic, optionally substituted, saturated alkyl group bonded to an oxygen atom. For example, an alkoxy radical may be a methoxy, ethoxy, propoxy or isopropoxy radical. , n-butoxy, tert-butoxy, neopentoxy, n-hexoxy, or a similar radical. By "aryl" group is meant an optionally substituted aromatic hydrocarbon. For example, an aryl group may be a phenyl group, a benzyl group, a tolyl group, a xylyl group, vinylbenzene ,. For the purposes of the invention, the halogen atom may be chosen from the group comprising fluorine, chlorine, bromine and iodine. The term "substituted" refers for example to the replacement of a hydrogen atom in a given structure with a group as defined above. When more than one position may be substituted, the substituents may be the same or different at each position. In the context of the present invention, "switching (English switch)" means the alternation between the reduced non-conductive (or insulating) state and the conductive oxidized state of the organic compounds according to the invention. For the purposes of the invention, the term "polymer" means a sequence of at least two compounds, identical or different, natural or synthetic. This sequence can be linear or branched. The term "polymer" includes oligomers, homopolymers as well as copolymers. For the purposes of the invention, the term "electroactive or electroactivity" refers to a state in which an exchange of electrons occurs. More particularly, an electroactive layer designates a layer capable of alternating between two different conduction states, in particular between the nonconductive (or insulating) reduced state and the conductive oxidized state. According to a first embodiment of the invention, the compounds of the invention may be of formula (I) in which: R 1 represents a hydrogen atom, a halogen atom, a hydroxyl group, a Cl-group, C4 alkoxy, a group -COOR3, a group - COR3, a group -SR3, a group -SeR3, a group -Si (OR3), a group - NR3R4, a group -CEN, a group -N3, a group -CEC -H a heterocycle selected from the group comprising pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a polyethylene group of the formula OO-CH 2 -CH 2 -p-, a C 1 -C 10 alkyl group, a phenyl group, polyethylene, alkyl, phenyl groups being optionally substituted by one or more groups selected from the group consisting of: -COOR3 group, -COR3 group, hydroxyl group, C1-C4 alkoxy group, -CONR3R4, -NR3R4 group; R2 represents a phenyl group, an -NH2 group, an aniline group, a meta-toluidine group, an anisidine group, a metatrifluoromethylaniline group, a para-phenylenediamine group (PPD), an amino-4-diphenyl group, these groups being optionally substituted with one or more groups selected from C 1 -C 4 alkyl, COOR 3, -COR 3, hydroxyl, C 1 -C 4 alkoxy, -CONR 3 R 4, diazo (N 2 +) a group -NO2, a group - NR3R4; X, Y and Q represent, independently of one another, O, S, NR3; Z represents a heterocycle selected from the group consisting of pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted with one or more groups selected from the group consisting of: - a C1-C10 alkyl group, a carboxyl, a group - COOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0,1,2,3; ρ = 0.1,2,3,4,5; q = 0.1; ## STR5 ## A and B represent, independently of one another, a C 1 -C 10 alkyl group; or q = 0, A represents a -CH 2 - group and forms a direct bond with Y to give a 5-membered heterocycle; or q = 1, A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; or io = q, A and B together with X and Y to which they are attached form a 7-membered heterocycle, wherein A is -CH 2 - and B is -CH 2 -CH 2 -, or B is a group -CH2 and A - CH2-CH2-; with the proviso that when q = 1, X = Y = O, Q = S, A and B together with X and Y to which they are attached form a 6-membered heterocycle in which A and B each represent - (CH 2) R 1 represents a hydrogen atom, R 2 represents an aniline group, m = 0, then n is different from 1. According to a second embodiment, the compounds of the invention may be of formula (I), in which R 1 represents a hydrogen atom, a halogen atom, a hydroxyl group, a Cl-C 4 alkoxy group, a -COOR 3 group, a COR 3 group, a -SR 3 group, a -SeR 3 group, a group Si (OR3), a group -NR3R4, a group -C = N, a group -N3, a group -C = CH a heterocycle selected from the group comprising pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyri midine, ferrocene, cobaltocene, a polyethylene group of the formula 0O-CH 2 -CH 2 -h-, a C 1 -C 10 alkyl group, a phenyl group, said polyethylene, alkyl, phenyl groups being optionally substituted by one or more groups selected from the group consisting of: - a group -COOR3, a group -COR3, a hydroxyl group, a C1-C4 alkoxy group, -CONR3R4, -NR3R4; R2 represents a phenyl group, an -NH2 group, an aniline group, a meta-toluidine group, an anisidine group, a meta-trifluoromethylaniline group, a para-phenylenediamine group (PPD), an amino-4-diphenyl group, these groups being optionally substituted with one or more groups selected from C1-C4 alkyl, -COOR3, -COR3, hydroxyl, C1-C4 alkoxy, -CONR3R4, diazo (N2 +), a group -NO2, a group -NR3R4; X and Y are O; Q is S; Z represents a heterocycle selected from the group comprising pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted by one or more groups selected from the group consisting of: - a C1-C10 alkyl group, a carboxyl group a group - COOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0,1,2,3; ρ = 0.1,2,3,4,5; q = 0.1; q = 1, A and B represent, independently of one another, a C 1 -C 10 alkyl group; or q = 0, A represents a -CH 2 - group and forms a direct bond with Y to give a 5-membered heterocycle; or q = 1, A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; or where q = 1, A and B together with X and Y to which they are attached form a 7-membered heterocycle, wherein A is -CH 2 - and B is -CH 2 -CH 2 -, or B is -CH2- group and A - CH2-CH2- group; it being understood that when q = 1, A and B together with X and Y to which they are bonded form a 6-membered heterocycle in which A and B each represent - (CH2) -, R1 represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is different from 1. According to a third embodiment of the invention, the compounds of the invention may be of formula (I), in which: R 1 represents an atom hydrogen, a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a -COOR3 group, a - COR3 group, a -SR3 group, a -SeR3 group, a -Si (OR3) group, a group - NR3R4, -CEN group, -N3 group, -CEC-H group, a heterocycle selected from the group consisting of pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole , oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimid ferrocene, cobaltocene, a C1-C10 alkyl group, a phenyl group, said polyethylene, alkyl, phenyl groups being optionally substituted with one or more groups selected from the group consisting of: - a group -COOR3, a group -COR3, a hydroxyl group, a C1-C4 alkoxy group, -CONR3R4, -NR3R4; R2 is phenyl, -NH2, aniline, meta-toluidine, anisidine, metatrifluoromethylaniline, paraphenylenediamine (PPD), amino-4-diphenyl, optionally substituted with one or more groups selected from C1-C4 alkyl, -COOR3, -COR3, hydroxyl, C1-C4 alkoxy, -CONR3R4, diazo (N2 +), a group -NO2, a group - NR3R4; X and Y are O; Q is S; Z represents a heterocycle selected from the group comprising pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted by one or more groups selected from the group consisting of: - a C1-C10 alkyl group, a carboxyl group a group - COOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0.1,2,3; where A and B together with X and Y to which they are attached together form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; it being understood that when R1 represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is different from 1. According to a fourth embodiment of the invention, the compounds of the invention may be formula (I), wherein: R1 represents a hydrogen atom, thiophene; R2 is aniline, phenyl substituted with diazo (N2 +), phenyl substituted with -NO2; ; X and Y are O; Q is S; Z represents thiophene; N = 1.2.3; m = 0.1; where A and B together with X and Y to which they are attached together form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; It being understood that when R1 represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is not 1.

The compounds according to the invention offer several advantages over the organic compounds conventionally used. As already indicated, the compounds according to the invention can form one or more layers or films that can be grafted or deposited on any type of substrates, whether insulating or conductive, rigid or flexible. The thickness of these layers or films can be modulated according to the nature of the organic compounds and / or according to whether they are deposited or grafted. Thus, the thickness of these layers or films may be for example between 1 and 100 nm, for example between 1 and 20 nm, for example between 1 and 5 nm when it is grafting by a reaction. reduction of the organic compounds of the invention (reductive route), but may also be between 10 nm and 1000 nm, for example between 1 nm and 10,000 nm, for example between 1 and 1000 nm, for example between 1 and 100 nm, when it is a deposit by an oxidation reaction of said compounds (oxidative route). These layers, preferably having a homogeneous thickness, have the property of being electroactive and switching between an insulative state and a conductive state. As indicated, the formation of these layers can take place reductively or oxidatively. The bond between the surface of the substrates and the compounds according to the invention may be of a strong nature (grafting by reduction) or of a less strong nature (deposition by oxidation). Whether grafted or deposited, said layers have good adhesion with the surface of the substrate. However, when the formation of the layers takes place by grafting, the adhesion of said layers to the substrates is better. The compounds according to the invention therefore allow control of the interface between the substrate and the layer or film. In the case of reduction grafting, the grafted molecules lead to films having the ability to switch between an insulating state and a conductive state comparable to that observed with conventional known organic compounds obtained by oxidative deposition. However, unlike the organic compounds of the state of the art, the compounds of the invention make it possible to modulate, in a significant manner, the electric potential window allowing this switching while allowing a strong grafting on the substrate. The switching potential of these layers can be, for example, between -0.5 volts and +1 volts, for example between -0.3 volts and +1 volts, for example between 0 volts and +1 volts, and between 0 volts and +0.5 volts versus a calomel electrode. The invention also relates to the processes for preparing the compounds according to the invention.

According to a first variant, the invention relates to a process for preparing a compound of formula (I) in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least one a palladium catalyst to obtain the compound of formula (I): XY Hal.4 Z1-R2 m + R1 with X, Y, Q, Z, R1, R2, n, m, q, A and B as defined previously; Hal represents a halogen atom; Wherein T represents a hydrogen atom or a group -B (OR ') (OR ") in which - R' and R" represent, independently of one another, a hydrogen atom, an alkyl group C1-C6, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl, or - R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more alkyl groups In a second variant, the invention relates to a process in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least one palladium catalyst in order to obtain the Compound of formula (IV), which compound (IV) provides compound (I) after reduction: ## STR1 ## (XYA (B) q A (B) q (III) (IV) NO 2 + R 1 m T 2 -NH 2 m R 1 A (B) q (I) with X, Y, Q, Z, R 1, n, m, q, A and B as defined above; Hal represents an atom of halogen; T represents a hydrogen atom or a group e -B (OR ') (OR ") in which - R' and R" represent, independently of one another, a hydrogen atom, a C 1 -C 6 alkyl group, an aryl group selected from the group consisting of a group comprising benzyl, phenyl, tolyl, xylyl, or - R 'and R "together form a 5- or 6-membered ring optionally substituted with one or more C 1 -C 4 alkyl groups. In both variants, the reaction of the halogenated compound (II) with the compound of formula (III) can be carried out in the presence of a palladium (Pd) catalyst. The palladium catalyst may be selected from the group consisting of, for example, palladium (0) tetrakis (triphenylphosphine), palladium (0) 1,2-bis (diphenylphosphino) ethane], palladium (II), palladium (II) propionate, palladium (II) chloride, palladium (II) bromide, palladium (II) acetylacetonate, palladium di (benzylidene acetate) (0) , palladium on carbon, palladium on alumina.

Said reaction may be carried out in a solvent or a mixture of polar solvents chosen from the group comprising, for example, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetonitrile, acetate ethyl, triethylamine, pyridine, diethyl ether, THF, diglyme, triglyme, dichloromethane, chloroform, acetone, butanone. In both variants, the reaction of the halogenated compound (II) with the compound of formula (III) can also be carried out in an ionic liquid chosen from ionic liquids comprising an imidazolium such as for example 1-N-butyl-3-methylimidazolium tetrafluoroborate. Said reaction can be carried out in the presence of a base selected from the group comprising, for example, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogen carbonate, triethylamine, potassium phosphate, silver oxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, barium hydroxide, cesium fluoride, sodium ethoxide . The compound (II) reacts with the compound (III) at a temperature of at least 20 ° C, for example between 40 and 140 ° C, for example between 60 and 120 ° C. The duration of said reaction varies depending on the compounds of formulas (II) and (III), the palladium catalyst and the solvent used. It can range from minutes to days. It can range, for example, from 30 minutes to 5 days, for example from 1 hour to 3 days. In the first variant, the compound (I) is obtained at the end of the reaction of the compound (II) with the compound (III), and can be used as it is or after purification by known methods. In the second variant, the compound of formula (IV) is obtained at the end of the reaction between the compounds of formulas (II) and (III). Compound (I) can then be obtained after reduction of said compound of formula (IV). The reduction of the compound of formula (IV) may be a hydrogenation reaction. The hydrogenation catalyst is advantageously chosen from palladium, rhodium and nickel catalysts, for example Lindlar's catalyst, palladium on carbon, palladium on calcium carbonate, palladium on alumina and palladium hydroxide. on charcoal, palladium (II) acetate, palladium (II) propionate, palladium (II) chloride, palladium bromide, Wilkinson catalyst and Raney nickel. The reduction can also be done using a hydride. The hydride may be a hydride selected from the group consisting of AlH 3 / AlCl 3, sodium dihydro (trithio) borate (NaBH 2 S 3), NaBH 4 catalyzed by NiCl 2 (PPh 3) 2 or CoCl 2. The reduction can also be carried out by the action of a metal in an acid medium. The metal may be zinc, tin or iron. The acid may be for example sulfuric acid, hydrochloric acid, nitric acid. The reduction of the compound of formula (IV) can also be carried out by the action of hydrazine in the presence of a catalyst. The catalyst may advantageously be chosen from catalysts comprising palladium, nickel, iron, zinc or carbon. Still in the second variant, the compound (I) can be obtained after reduction of said compound of formula (IV), for example, by action of the dodecacarbonyl trifer [Fe3 (CO) 12] complex in an alcoholic medium. The alcoholic medium may be one or a mixture of alcohols selected for example from methanol, ethanol or isopropanol. The reduction of said compound of formula (IV) can also be carried out by the action of sulfides. The sulfide may be selected from sodium hydrosulfide, ammonium sulfide or polydisulfide. The reduction may, in addition, be carried out electrochemically in an acid medium or in a micellar medium, among the surfactants used may be of anionic, cationic or neutral nature. The reduction reaction of the compound of formula (IV) to yield compound (I) may be carried out in a suitable solvent mixture (s) selected from the group comprising, for example, water, hydrazine, methanol, ethanol, isopropanol, methanoic acid, acetic acid, THF, dichloromethane, chloroform, carbon tetrachloride, N, N-dimethylformamide (DMF), ethyl acetate, benzene, toluene or dioxane. The reduction reaction is advantageously carried out at the reflux temperature of the solvent or solvent mixture.

The duration of the reduction reaction is variable and can range, for example, from 30 minutes to 6 hours. The compound of formula (I) obtained at the end of the reduction may be used as it is or may be purified by known purification methods.

The halogenated compounds of formula (II) may be prepared by any suitable halogenation process for the halogenation of a compound of formula (V) [Z -] - m R2 (V) wherein Z, m and R2 are such than previously defined. The halogenation reaction may be carried out by the action of a halogenating agent selected from the group consisting of, for example, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, chlorine, bromine, bromine, and the like. iodine, sulfuryl chloride, hypochlorous acid, hydrobromic acid, magnesium bromide, magnesium iodide. The halogenation reaction may be carried out in the presence of a metal selected from the group consisting of, for example, zinc, mercury oxide, mercury acetate. The boronic esters of formula (VIII) correspond to the compounds of formula (III) in which T represents a group -B (OR ') (OR "). When said boronic esters of formula (VIII) are not marketed, they may be prepared, for example, by a process in which a compound of formula (VI) is reacted with a borate of formula (VII): ## STR2 ## GOLD OR "(VII) A (B) q A (B) q (VI) (VIII) wherein X, Y, Q, R1, n, q are as defined above; R" 'represents a d hydrogen, a C1-C6 alkyl group, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl; R 'and R "represent, independently of each other, a hydrogen atom, a C 1 -C 6 alkyl group, an aryl group selected from the group comprising benzyl, phenyl, tolyl and xylyl; or - R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more C 1 -C 4 alkyl groups. The reaction between the compounds of formulas (VI) and (VII) can be carried out at a temperature ranging from -85 to 25 ° C. The duration of this reaction can be between 30 minutes and 5 hours. The reaction between a compound of formula (VI) with a borate of formula (VII) may be carried out in one or a mixture of polar solvents chosen from water, N, N-dimethylformamide (DMF) dimethylsulfoxide (DMSO), N-methylpyrrolidinone, ethanol, propanol, isopropanol, acetonitrile, ethyl acetate, diethyl ether, THF, dioxane, anisole, ethylene glycol dimethyl ether, diglyme, triglyme, dichloromethane, chloroform, acetone, butanone. Once prepared, the organic compounds of formula (I) are capable of forming layers deposited or grafted onto the surface of the substrates by reduction or oxidation. The reduction or oxidation can be carried out electrochemically or by chemical reactions. In the latter case, any oxidant or reductant having a standard redox potential respectively greater than or less than the standard redox potential of the compound of formula (I) may be used. The deposition or grafting may be carried out in a polar solvent or in a mixture of solvents chosen from the group comprising, for example, water, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N-dimethylformamide (DMF), methylpyrrolidinone, ethanol, propanol, isopropanol, acetonitrile, ethyl acetate, diethyl ether, THF, dioxane, anisole, ethylene glycol, dimethyl ether, diglyme, triglyme, dichloromethane, chloroform, acetone, butanone.

The deposition or grafting of the organic compounds of formula (I) on the surface of the substrates may also be carried out in an ionic liquid chosen from ionic liquids comprising imidazolium, for example 1-N-butyl-3-methylimidazolium tetrafluoroborate.

The reduction or oxidation reactions allowing the grafting or deposition of the layers, whether chemical or electrochemical, can be carried out in a micellar medium using surfactants of anionic, cationic or neutral nature. Deposition or grafting of the layers by oxidation or grafting reactions, whether they are carried out chemically or electrochemically, can also be carried out in aqueous medium in the presence of cyclodextrins of variable size added in order to solubilize the organic compounds of formula (I). The processes for preparing the organic compounds of formula (I) as well as the deposition or grafting of said compounds on the surface of the substrates in the form of one or more layers have the advantage of being easy to implement, reproducible, industrially feasible and economically interesting. The subject of the invention is the use of a compound of formula (I) as defined above, in plastic electronics, in molecular electronics, as a layer for insulating, semiconducting and conductive surfaces. More particularly, the compounds of the invention can be used to produce organic light-emitting diodes, transparent electrodes, organic photovoltaic cells, organic transistors, single-electron transistors, sensors and biosensors. The invention also relates to the use of a compound the use of a compound of formula (I) as defined above, for producing anticorrosion coatings, surfaces with switchable wetting properties, self-lubricating surfaces, electrochromic coatings intelligent coatings, ie coatings whose properties can be switched reversibly with the aid of the external stimulus, adhesion primers, that is to say, layers which allow the adhesion and adhesion of a second layer of variable chemical nature but which would not have been adherent if this second layer had been deposited directly on the substrate. The invention also extends to the use of a compound the use of a compound of formula (I) as defined above, in the field of energy storage as electrode materials for batteries, or supercapacitors which are electrical storage systems that can deliver large amounts of energy in a short period of time, especially as layers deposited on carbon nanotubes. Another object of the present invention is a material comprising a compound of formula (I) as defined above. The materials according to the invention can be prepared by known methods. The present invention, according to another of its aspects, also relates to an article comprising a compound of formula (I) according to the invention as defined above.

EXAMPLES Solvents and Reagents Toluene is distilled under argon on sodium; tetrahydrofuran (THF) is distilled under argon on sodium and benzophenone. The other solvents used come from the VWR supplier.

Nuclear Magnetic Resonance (NMR) The 1H and 13C spectra are carried out with a Bruker Avance I I I 300 MHz and 400 MHz apparatus. The chemical shifts (8) of the 1 H NMR and 13 C NMR spectra are calibrated on the reference value of the solvent as described in the article Gottlieb et al, J. Org. Chem., 1997, 62, 7512. Measurements are made at 25 ° C in 5 mm diameter tubes. The spectra are carried out in deuterated solvents from the Eurisotop supplier. The coupling constants are given in Hertz.

Chromatography Thin layer chromatography (TLC) is carried out on aluminum plates "TLC Silica Gel 60F254" from Merck. The compounds are revealed under UV lamp at 254 or 326 nm.

The chromatographic columns are made with silica gel (Silica gel 60 (40-63 μm) from Merck.

Mass Spectrometry The mass spectra were recorded on a Finigan 5890 spectrometer coupled to a DSQ1 in Electronic Impact mode, in "Analytical" quality solvents.

Synthesis of precursors 1- (Thien-2-yl) -4-nitrobenzene and 1- (3,4-ethylenedioxythien-2-yl) -4-nitrobenzene were prepared according to the protocols described in references [1] and [2]. The biEDOT was synthesized according to the procedure described in reference [3].

Example 1: General procedure for the iodination of thiophene derivatives To a suspension of a thiophene derivative (8 mmol) in acetic acid (150 mL), mercury oxide (1.04 equivalents; 32 mmol) and iodine (1.02 equivalents, 8.16 mmol) is added. The mixture is degassed in an ultrasonic bath for 20 minutes and then stirred overnight. The precipitate is filtered and then dissolved in dichloromethane. The organic phase is washed successively with a solution of potassium iodide, a solution of sodium bicarbonate (NaHCO3) and water. After drying over magnesium sulfate, the solvent is evaporated under vacuum. The product is used without further purification.

1- (5-iodothien-2-yl) -4-nitrobenzene 90% NO2 c b The iodinated thiophene derivative was prepared according to the general procedure for iodination indicated above, with 7 mmol of thiophene derivative. Yield: 2.10 g; 90%. A yellow powder is obtained.

1 H NMR (300 MHz, CDCl 3) δ 7.13 (d, 1H, J = 3.6 Hz); 7.30 (d, 1H, J = 3.6 Hz); 7.66 (d, 1H, J = 8.4 Hz, CHU); 8.23 (d, 1H, J = 8.4 Hz, CHb). 13C NMR (75 MHz, CDCl3) δ 76.1 (CH); 124.5 (Cc); 125.9 (Ob); 127.0 (Cf); 138.5 (Cg); 139.4 (Ca); 146.9 (Cd); 147.5 (Ce). MS: M calc. 331; found: [M] + 331. 1- [1- (5-Iodo-3,4-ethylenedioxythien-2-yl) -4-nitrobenzene] O00 NO2 98% cb The iodinated EDOT derivative was prepared according to the general procedure. for the iodination indicated above, from 6.57 mmol of 3,4-diethylenedioxythiophene derivative (EDOT). Yield: 2.52 g; 98%. A yellow powder is obtained. 1H NMR (300 MHz, CDCl3) δ 4.37 (m, 4H); 7.78 (d, 1H, J = 9.2 Hz); 8.21 (d, 1H, J = 9.2 Hz). 13 C NMR (75 MHz, CDCl 3) δ 52.1 (CH); 64.9 and 64.9 (Cf and Cg '); 120.4 (Ce); 124.2 (Ch); 125.7 (Cc); 139.0 (Ca); 139.6 (Cf or Cg); 145.0 (Cf or Cg); 145.7 (Cd). MS: M calculated 389; found: [M] + 389.

Example 2: General procedure for the synthesis of the boronic ester [4] Under an argon atmosphere, a solution of the thiophenic compound (30 mmol) in distilled THF (100 mL), with stirring, is cooled to -78 ° C. ° C. A solution of 2.5 M butyllithium (12 mL, 1 equivalent) is added dropwise and the resulting solution is stirred at -78 ° C for one hour. The triisopropylborate (21 mL, 3 equivalents) is added and the reaction mixture is allowed to come to room temperature (20 ° C.). After 2.5 h, a solution of pinacol (10.6 g) in THF (30 mL) is added. The reaction mixture is stirred for 30 minutes and the solvent is then evaporated under vacuum. The residue is dissolved in diethyl ether, washed twice with water and dried over MgSO4. The solvent is evaporated under vacuum. The product is used without further purification. This compound was prepared according to the general procedure above for the synthesis of the boronic ester, at room temperature, at room temperature, and at room temperature. from 30 mmol of thiophene. Yield: 5.3 g; 85%. A white powder is obtained. 1 H NMR (300 MHz, CDCl 3) δ 1.36 (s, 12H, CH 3); 7.20 (dd, 1H, J = 3.6 and 4.8 Hz, H4); 7.64 (d, 1H, J = 4.8 Hz, H5); 7.66 (d, 1H, J = 3.6 Hz, H3). 13 C NMR (75 MHz, CDCl 3) δ 24.8 (CH 3); 84.1 (C-OB); 128.2 (C3); 132.4 (C4); 137.2 (C5). MS: M calculated 210; found: [M] + 210. 2- (2,3-Dihydrothieno [3,4-b] [1,4] dioxin-5-yl) -4,4,5,5-tetramethyl-2-thiophen-2 This compound was prepared according to the above general procedure for the synthesis of the boronic ester with 50 mmol of EDOT.

Yield: 11.13 g; 85%. A white powder is obtained. 1 H NMR (300 MHz, CDCl 3) δ 1.34 (s, 12H, CH 3); 4.17-4.20 (m, 2H, OCH2); 4.29-4.31 (m, 2H, OCH2); 6.63 (s, 1H, CHedot). 13 C NMR (75 MHz, CDCl 3) δ 24.7 (CH 3); 64.3 (CH2-0); 65.1 (CH2-0); 83.8 (C-5 OB); 107.5 (CHedot); 142.3 and 149.0 (C3-O and C4-O). MS: M calculated 268; found: [M] + 268.

4,4,5,5-tert-thiazol-2- (2,2 ', 3,3'-tetrahydro-5,5'-bithieno [3,4-b] (1, 4) dioxin-5-yl) This compound was prepared according to the above general procedure for the synthesis of the boronic ester, starting from 10 mmol of bi-EDOT. Yield: 3.94 g 93% A green solid is obtained: 1 H NMR (300 MHz, CDCl 3) δ 1.28 (s, 12H, CH 3) 4.23-4.25 (m, 2H, OCH 2) 4.32-4.34 (m, 6H, OCH 2) 6.31 (s, 1H) 13C NMR (75 MHz, CDCl3) 8 24.5 (CH3) 64.6 (CH2-O) 65.0 (CH2-O) 83.2 (COB) 97.5 (CHedot) 109.9 (CS) 137.0 and 141.2 (CO) MS: M calculated 408, found: 408.

Example 3: General procedure for the Suzuki coupling reaction [4] The boronic derivative (2 mmol), the halogenated derivative (2 mmol), sodium carbonate (3 equivalents, 6 mmol), palladium tetrakis (triphenylphosphine) (Pd °) (5%) are successively introduced into a Schlenk containing 25 ml of N, N-dimethylformamide (DMF). The reaction mixture is heated at 110 ° C for 2-3 days. After cooling to room temperature (20 ° C.), the solvent is evaporated under vacuum.

The brown residue is dissolved in dichloromethane, washed twice with water, dried over MgSO4 and concentrated. The crude product is purified by chromatography on silica gel. 2- (4-Nitrophenyl) -3,4-ethylenedioxythiophene NO 2 OO cb NO 2 The nitrophenyl-EDOT compound was prepared by the procedure indicated above, with 15 mmol of boronic derivative (chromatography eluent: petroleum ether / dichloromethane 3 / 7t). Yield: 2.79 g; 70%. A yellow powder is obtained. 1H NMR (400MHz, CDCl3) δ 4.28-4.40 (m, 2H, Hg '); 4.37-4.40 (m, 2H, Hf '); 6.48 (s, 1H, Hh); 7.86 (d, J = 9.0 Hz, 2H, Ha); 8.17 (d, J = 9.0 Hz, 2H, Hb). 13 C NMR (100 MHz, CDCl 3) 64.3 (OC 6 H 2); 65.1 (OCf'H2); 101.0 (Ch); 124.1 (Ch); 125.7 (Cg); 139.8 (Ca); 140.9 (Cg); 142.9 (Cf); 145.8 (Cd). MS: M calculated 263; found: 263. Elemental Analysis: Calculated: C 54.75, H 3.45, N 5.32, S 12.18; found: C 55.04, H 3.50, N 6.05, S 10.88.

2- (4-Nitrophenyl) -3,4,3 ', 4'-bis (ethylenedioxy) -5,2'-bithiophene NO2 36% 9' / - OO + 20 NO2 The nitophenyl-bi-EDOT compound was prepared by the general procedure described above, with 2 mmol of boronic derivative. The product was purified by chromatography on silica gel using a 3/7 mixture of petroleum ether / dichloromethane as eluent.

Yield: 316.3 mg; 36%. A dark powder is obtained. 1 H NMR (400 MHz, CDCl 3) δ 4.23-4.27 (m, 2H, OCH 2); 4.36-4.40 (m, 6H, 3x OCH2); 6.36 (s, 1H, Hi); 7.84 (d, J = 9.2 Hz, 2H, Ha); 8.17 (d, J = 9.2 Hz, 2H, Hb). 13 C NMR (100 MHz, CDCl 3) δ 63.9, 64.0, 64.4 and 64.7 (4 x OCH 2); 98.6 (Ci); 108.8, 111.5, 111.7 (Cei Ch and C;); 123.4 (Ch); 124.7 (Ce); 136.7, 137.4, 139.8, 140.7 (Cf, Cg, C 1, Ck), 139.3 (Ca); 144.4 (Ob); 145.0 (Cd). MS C18H13NO6NaS2 [M + Na +]: Calcd: 426.0082, Found: 426.0093. Elemental Analysis: Calculated: C 53.59, H 3.25, N 3.47, S 15.89; found: C 54.74, H 3.54, N 3.60, S 14.02. 2- (4-Nitrophenyl) -3 ', 4'-ethylenedioxy-5,2'-bithiophene 78% 2- (4-nitrophenyl) -3', 4'-ethylenedioxy-5,2'-bithiophene was prepared according to the general procedure described above, starting from 4 mmol of boronic derivative (chromatographic eluent: mixture of petroleum ether / dichloromethane 25/75). Yield: 1.38g; 78%. An orange powder is obtained. 1 H NMR (400 MHz, CDCl 3) δ 4.28-4.31 (m, 2H, OCH 2); 4.40-4.42 (m, 2H, OCH2); 6.23 (s, 1H, Hi); 7.25 (d, J = 4.0 Hz, 2H, Hfor Hg); 7.41 (d, J = 4.0 Hz, 2H, Hfor Hg); 7.73 (d, J = 8.8 Hz, 2H, Ha); 8.24 (d, J = 8.8 Hz, 2H, Hb). 13 C NMR (100 MHz, CDCl 3) δ 64.6 and 65.2 (2 x OCH 2); 98.1 (Ci); 111.7 and 138.4 (Ciand Ck); 123.9 and 126.0 (Cf and Cg); 124.5 (Ob); 125.4 (Cc); 137.6 and 139.0 (Ch and C;); 140.6 (Ca); 142.0 (Ce); 146.3 (Cd). MS C16H11NO4S2 [M + H +]: calculated: 345.0130, found: 345.0145. Elemental analysis C 16 H 11 NO 4 S 2: calculated: C 55.64, H 3.21, N 4.06, S 18.56, found: C 55.04, H 3.13, N 4.22, S 17.97.

2- (4-Nitrophenyl) -3,4-ethylenedioxy-5,2'-bithiophene 2- (4-nitrophenyl) -3,4-ethylenedioxy-5,2'-bithiophene was prepared according to the general procedure described above. previously for the Suzuki coupling reaction, with 2 mmol boronic derivative (chromatography eluent: 25/75 petroleum ether / dichloromethane mixture). Yield: 690 mg; 63%. An orange powder is obtained. 1 H NMR (400 MHz, CDCl 3) δ 4.43 (s, 4H, 2 x OCH 2); 7.08 (dd, 1H, J = 3.2 and 5.2Hz, CHk); 7.30 (d, 1H, J = 5.2 Hz, CHI); 7.34 (d, 1H, J = 3.2 Hz, CHI); 7.86 (d, 1H, J = 8.8 Hz, CHI); 8.18 (d, 1H, J = 8.8 Hz, CHb).

13C NMR (100 MHz, CDCl3) 64.7 and 65.0 (2 x OCH2); 112.1 (Ce); 113.8 (Ci); 124.0 (Ci); 124.1 (Ch); 125.0 (Ci); 125.6 (Ce); 127.4 (Ck); 133.9 (Ch); 137.9 and 140.9 (Cf and Cg); 139.4 (Ca); 145.3 (Cd). MS C16H11NO4S2 [M +]: calcd: 345.0130, found: 345.0139. Elemental analysis C16H11NO4S2: calculated: C 55.64, H 3.21, N 4.06, S 18.56; Found: C 55.27, H 3.21, N 4.09, S 17.70.

2- (4-Nitrophenyl) -3,4,3 ', 4', 3 ", 4" -ter (ethylenedioxy) -5,2 ', 5', 2 "-terthiophene The nitrophenyl-terEDOT compound was prepared according to the general procedure described above for the Suzuki coupling reaction with 2 mmol of boronic derivative The product was purified by chromatography on alumina using dichloromethane as eluent Yield: 465 mg, 71%. A dark powder is obtained.1H NMR (400MHz, CDCl3) 4.26 (m, 2H, OCH2) 4.30-4.50 (m, 10H, 5x25 OCH2) 6.33 (s, 1H, CH2); , 2H, J = 8.8 Hz, CHI); 8.19 (d, 2H, J = 8.8 Hz, CHb). Cb OO / - \ P 'n' OOO ~ n O g O c 7 'n \ m nir 17 % m / - MSc24H17NO8S3 [M + H +]: calcd: 543.0116, found: 543.0126

Example 4: General Procedure for the Reduction of the Nitro (NO2) Function to Amine (NH2) [5] Palladium (10%) on charcoal (0.086 mmol, 10%) and hydrazine (1 ml) are added to a solution of the nitro derivative (0.86 mmol) in THF (20mL). The reaction mixture is refluxed for 4 hours. After cooling to room temperature (20 ° C.), the suspension is filtered on celite and then the solvent is evaporated under vacuum. The dissolved residue in dichloromethane is washed with water and then dried over magnesium sulfate. The product is used without further purification. 2- (4-Aminophenyl) -3,4,3 ', 4'-bis (ethylenedioxy) -5,2'-bithiophene The amine derivative was prepared from 1 mmol of nitro derivative, according to the general procedure for the reduction of the nitro function to amine indicated above. Yield: 124 mg; 76%. A red powder is obtained. 1 H NMR (300 MHz, CDCl 3) δ 3.70-3.73 (broad s, 2H); 4.24-4.27 (m, 2H); 4.33- 4.37 (m, 6H); 6.27 (s, 1H); 6.69 (d, 2H, J = 8.4 Hz); 7.55 (d, 2H, J = 8.4 Hz). 13 C NMR (75 MHz, CDCl 3) 64.6, 64.6, 64.9 and 65.0 (4 x CH2O); 97.3 (C1H); 106.2 (C1 or Ch); 110.2 (C1 or Ch); 115.2 (CbH); 115.8 (Ce); 123.7 (Ca); 127.3 (CM); 136.3, 136.7, 137.5 and 141.3 (Cf, Cg, Ci and Ck); 145.0 (Cd). MS C18H15NO4NaS2 [M + H +]: calculated: 374.0521, found: 374.0515. Elemental analysis C12H11NO2S: calculated: C 57.89, H 4.05, N 3.75, S 17.17; found: C 58.50, H 4.33, N 3.93, S 15.95.

2- (4-Aminophenyl) -3 ', 4-thiohexyl-5,2-bithiopathene 83% NH2 The amine derivative was prepared from 0.6 mmol of nitro derivative, according to the procedure general for the reduction of the nitro function to amine indicated above.

Yield: 189 mg; 83%. A yellow powder is obtained. 1H NMR (300 MHz, CDCl3) δ 4.76 (s, 2H); 4.25-4.27 (m, 2H, Hi '); 4.34-4.37 (m, 2H, Hk '); 6.20 (s, 1H, Hi); 6.68 (d, 2H, J = 8.8 Hz, Hb); 7.06 (d, 1H, J = 4.0 Hz, Hf), 7.14 (d, 1H, J = 4.0 Hz, Hg); 7.41 (d, 2H, J = 8.8 Hz, Ha). 13 C NMR (75 MHz, CDCl 3) 64.6 (OCIH 2); 65.0 (Ck'H2); 96.5 (Ci); 112.6 (C1); 115.3 (Ch); 121.3 (Cf); 123.8 (Cg); 125.0 (Ca); 126.8 (C); 132.4 (Ch); 137.2 (Ck); 141.9 (Ci); 143.2 (Ce); 145.9 (Cd). MS C16H9NO2S2 [M + H +] calculated: 316.0466, found: 316.0461. Elemental analysis C16H9NO2S2: calculated C 60.93, H 4.15, N 4.44, S 20.33; found: C 60.82, H 4.80, N 4.01, S 17.46. 2- (4-Aminophenyl) -3,4-ethylenedioxy-5,2'-bithiophene 95% 2 The amine derivative was prepared from 0.86 mmol of nitro derivative. according to the general procedure for the reduction of the nitro function to amine 20 indicated above. Yield: 270 mg; 95%. A yellow powder is obtained. 1H NMR (300 MHz, CDCl3) δ 4.32-4.35 (m, 2H); 4.37-4.39 (m, 2H); 6.70 (d, 2H, J = 8.8 Hz, Hb); 7.02 (dd, 1H, J = 3.6 and 5.0 Hz, Hk); 7.20 (d, 1H, J = 5.0Hz, H 1) 7.22 (d, 1H, J = 3.6Hz, Hi); 7.53 (d, 2H, J = 8.8 Hz, Ha).

13 C NMR (75 MHz, CDCl 3) δ 64.6 and 64.9 (2 x OCH 2); 108.3 (This gold Ch); 115.2 (Ch); 115.5 (Ca); 122.3 (Ci); 123.3 (Ci); 127.1 (Ck); 127.3 (Ce); 135.0 (C1); 136.7 (Cf or Cg); 137.9 (Cf or Cg); 145.3 (Cd). MS C16H9NO2S2 [M + H +]: Calcd: 316.0466, Found: 316.0466.

Elemental analysis. C 16 H 9 NO 2 S 2: calculated: C 60.93, H 4.15, N 4.44, S 20.33; found: C 61.11, H 4.61, N 4.62, S 17.95.

2- (4-aminophenyl) -3,4,3 ', 4', 3 ", 4" -ter (ethylene edioxy) -5,2 ', 5', 2 "-terthiophen The amine derivative was prepared from 0.11 mmol of nitro derivative, according to the general procedure for the reduction of the nitro function to the amine indicated above Yield: 56 mg, quantitative A red powder is obtained. MHz, CDCl3) δ 4.21-4.40 (m, 12H), 6.27 (s, 1H, CHp), 6.68 (d, 2H, J = 7.6 Hz, CHb), 7.55 (d, 2H, J = 7.6 Hz, CHU; MS: C24H19NO6S3 [M + H +]: calcd: 513.0374, found: 513.0371.

Example 5: Process for the preparation of 2- (4-nitrophenyl) -3,4,3 ', 4'-bis (ethylenedioxy) -5,2'-bithiophene [6] ## STR2 ## N O2 NO2 BiEDOT (2.2 g, 7.8 mmol, 1.3 eq.), 4-bromonitrobenzene (1.21 g, 6 mmol) and potassium acetate (1.76 g, 18 mmol, 3 eq.) Are successively introduced in a Schlenck containing 20 mL of DMF. After total dissolution of the reagents, palladium acetate (134 mg, 0.6 mmol, 0.1 eq.) Is added, then the reaction medium is heated at 80 ° C. for one hour. After returning to ambient temperature (20 ° C.), the red precipitate is filtered and washed with ethanol. The nitrated compound is subsequently used without further purification.

Yield: 72% Reference Lists [1] US 6130339 [2] US 6197921 B1 [3] G. A. Sotzing, J. R. Reynolds, P. J. Steel, Adv. Mater., 1997, 9, 10, 795-798. [4] M.Frigoli, C. Mostrou, Samat, A. Guglielmetti, Eur. J. Org. Chem., 2003, 2799-2812. [5] L. Flamigni, B. Venture, E. Baranooff, J-P. Collin, J-P. Wild, Eur. J. of Inorg. Chem., 2007, 33, 5189-5198. [6] A. Borghese, G. Geldhof, L. Antoine, Tetrahedron, 2006, 47, 9249-9252. i0

Claims (13)

REVENDICATIONS1. A compound of the formula (I): wherein R 1 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C 1 -C 4 alkoxy group, a -COOR 3 group, a group Io COR3, a group -SR3, a group -SeR3, a group -Si (OR3), a group -NR3R4, a group -CEN, a group -N3, a group -CEC-H, a heterocycle chosen from the group including pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a polyethylene group of formula ± O-CH2-CH2 a C1-C10 alkyl group, a phenyl group, said polyethylene, alkyl, phenyl groups being optionally substituted with one or several groups selected from the group consisting of: - a -COOR3 group, a -COR3 group, a hydroxyl group, a C1-C4 alco group xy, -CONR3R4, -NR3R4; R2 represents a phenyl group, an -NH2 group, an aniline group, a meta-toluidine group, an anisidine group, a metatrifluoromethylaniline group, a para-phenylenediamine group (PPD), an amino-4-diphenyl group, these groups being optionally substituted with one or more groups selected from C1-C4 alkyl, -COOR3, -COR3, hydroxyl, C1-C4 alkoxy, -CONR3R4, diazo (N2 +), group -NO2, a group -NR3R4; X, Y and Q represent, independently of each other, O, Se, S, Te, NR 3, P (O), P (R 3); Z represents a heterocycle selected from the group comprising pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted by one or more groups selected from the group consisting of: - a C1-C10 alkyl group, a carboxyl group a group - IoCOOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0,1,2,3; P = 0.1,2,3,4,5; q = 0.1; q = 1, A and B represent, independently of one another, a C 1 -C 10 alkyl group; or = O, A represents a -CH 2 - group and forms a direct bond with Y to give a 5-membered heterocycle; or q = 1, A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; or q = 1, A and B together with X and Y to which they are attached form a 7-membered heterocycle, wherein A is -CH 2 - and B is -CH 2 -CH 2 -, or B is a group -CH2- and A - CH2-CH2-; it being understood that when q = 1, X = Y = O, Q = S, A and B together with X and Y to which they are bonded form a 6-membered heterocycle in which A and B each represent - (CH 2) -, RI represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is different from 1. 2. A compound of formula (I) according to claim 1, wherein: R1 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a -COOR3 group, a - group. COR3, a group -SR3, a group -SeR3, a group -Si (OR3), a group -NR3R4, a group -CEN, a group -N3, a group -CEC-H a heterocycle selected from the group comprising pyrrole , furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine, phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a polyethylene group of formula ± O-CH 2 -CH 2 49-, a C 1 -C 10 alkyl group, a phenyl group, said polyethylene, alkyl, phenyl groups being optionally substituted with one or several groups selected from the group comprising: a -COOR3 group, a -COR3 group, a hydroxyl group, a 15-group C1-C4 alkoxy, -CONR3R4, -NR3R4; R2 represents a phenyl group, an -NH2 group, an aniline group, a meta-toluidine group, an anisidine group, a metatrifluoromethylaniline group, a para-phenylenediamine group (PPD), an amino-4-diphenyl group, these groups being optionally substituted; by one or more groups selected from C 1 -C 4 alkyl, COOR 3, -COR 3, hydroxyl, C 1 -C 4 alkoxy, -CONR 3 R 4, diazo (N 2 +), a group -NO2, a group -NR3R4; X, Y and Q represent, independently of one another, O, S, NR3; Z represents a heterocycle selected from the group consisting of pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted with one or more groups selected from the group consisting of: - an alkyl group CI-Clo, a group carboxyl, a COOR3 group, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0,1,2,3; ρ = 0.1,2,3,4,5; q = 0.1; ## STR5 ## A and B represent, independently of one another, a C 1 -C 10 alkyl group; or q = 0, A represents a -CH 2 - group and forms a direct bond with Y to give a 5-membered heterocycle; or q = 1, A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; where λ = 1, A and B together with X and Y to which they are attached form a 7-membered heterocycle, where A is -CH 2 and B is -CH 2 -CH 2 -, or B is a group -CH2- and A - CH2-CH2-; It being understood that when q = 1, X = Y = O, Q = S, A and B together with X and Y to which they are attached form a 6-membered heterocycle in which A and B each represent - (CH 2) R 1 represents a hydrogen atom, R 2 represents an aniline group, m = 0, then n is not equal to 1. 3. Compound of formula (I) according to one of claims 1 or 2, wherein: RI represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a group - COOR3, COR3, -SR3, -SeR3, -Si (OR3), -NR3R4, -C = N, -N3, -C = CH heterocycle selected from the group consisting of pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine , phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a polyethylene group of the formula 0O-CH 2 -CH 2 -), a C 1 -C 10 alkyl group, a phenyl group, said polyethylene groups, alkyl, phenyl being optionally substituted by one or more groups selected from the group consisting of: - a group -COOR3, a group -COR3, a hydrocyclic group oxyl, Cl-C4 alkoxy, -CONR3R4, -NR3R4; R2 represents a phenyl group, an -NH2 group, an aniline group, a meta-toluidine group, an anisidine group, a metatrifluoromethylaniline group, a para-phenylenediamine group (PPD), an amino-4-diphenyl group, these groups being optionally substituted; by one or more groups selected from C1-C4alkyl, -OCOR3, -COR3, hydroxyl, C1-C4alkoxy, -CONR3R4, diazo (N2 +), group -NO2, a group -NR3R4; X and Y are O; Q is S; Z represents a heterocycle selected from the group consisting of pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted by one or more groups selected from the group consisting of: - a C1-C10 alkyl group, a group carboxyl, a group -COOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0,1,2,3; P = 0.1,2,3,4,5; q = 0.1; ## STR5 ## A and B represent, independently of one another, a C 1 -C 10 alkyl group; or q = 0, A represents -CH 2 - and forms a direct bond with Y to give a 5-membered heterocycle; or q = 1, A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; or where q = 1, A and B together with X and Y to which they are attached form a 7-membered heterocycle, wherein A is -CH 2 - and B is -CH 2 -CH 2 -, or B is -CH2- group and A - CH2-CH2- group; it being understood that when q = 1, A and B together with X and Y to which they are bonded form a 6-membered heterocycle in which A and B each represent - (CH2) -, R1 represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is different from 1. i0 4. Compound of formula (I) according to any one of claims 1 to 3, wherein: R1 represents a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C4 alkoxy group, a group -COOR3, a group COR3, a group -SR3, a group -SeR3, a group -Si (OR3), a group -NR3R4, a group -CEN, a group -N3, a group -CEC-H, a heterocycle selected from the group consisting of pyrrole, furan, phosphole, thiophene, tetrathiafulvalene, selenophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, bipyridine, terpyridine , phenanthroline, pyrazine, pyridazine and pyrimidine, ferrocene, cobaltocene, a C1-C10 alkyl group, a phenyl group, said polyethylene, alkyl, phenyl groups being optionally substituted with one or more groups selected from the group comprising: - a group -COOR3, a group -COR3, a hydroxyl group, a C1-C4 alkoxy group, -CONR3R 4, -NR3R4; R2 is phenyl, -NH2, aniline, meta-toluidine, anisidine, metatrifluoromethylaniline, paraphenylenediamine (PPD), amino-4-diphenyl, optionally substituted with one or more groups selected from C1-C4 alkyl, -COOR3, -COR3, hydroxyl, C1-C4 alkoxy, -CONR3R4, diazo (N2 +), group -NO2, a group -NR3R4; X and Y are O; Q is S; Z represents a heterocycle selected from the group comprising pyrrole, furan, thiophene, selenophene, said heterocycle being optionally substituted by one or more groups selected from the group consisting of: - a C1-C10 alkyl group, a carboxyl group a group - IoCOOR3, a hydroxyl group, a C1-C4 alkoxy group, -NR3R4; R3 and R4 represent, independently of one another, a hydrogen atom, a C1-C6 alkyl group or a phenyl group; n = 1,2,3,4,5; m = 0,1,2,3; Wherein A and B together with X and Y to which they are attached form a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; with the proviso that when R1 is hydrogen, R2 is aniline, m = 0, then n is not 1. 5. Compound of formula (I) according to any one of claims 1 to 4, wherein: R1 represents a hydrogen atom, thiophene; R2 is aniline, phenyl substituted with diazo (N2 +), phenyl substituted with -NO2; ; X and Y are O; Q is S; Z represents thiophene; N = 1.2.3; m = 0.1; Where X and Y together are, with X and Y to which they are bound, a 6-membered heterocycle, wherein A and B each represent a -CH 2 - group; it being understood that when R1 represents a hydrogen atom, R2 represents an aniline group, m = 0, then n is not 1. 6. Process for the preparation of a compound of formula (I) according to any one of claims 1 to 5, in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least one palladium catalyst to obtain the compound of formula (I): wherein X, Y, Q, Z, R 1, R 2, n, m, q, A and B are such that defined in any one of claims 1 to 5; Hal represents a halogen atom; R represents a hydrogen atom or a group -B (OR ') (OR ") in which - R' and R" represent, independently of one another, a hydrogen atom, an alkyl group at C1-C6, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl, or - R 'and R "together form a 5- or 6-membered ring optionally substituted by one or more alkyl groups in CI-C4. 7. Process for the preparation of a compound of formula (I) according to any one of claims 1 to 5, in which a halogenated compound of formula (II) is reacted with a compound of formula (III) in the presence of at least one palladium catalyst to obtain the compound of formula (IV), which compound (IV) provides the compound (I) after reduction: Hal-EZ ~ NO2 + R1 m T - ~ R1 1 X YI A (B) q A (B) q (III) (IV) Z1-NO2 m R1 XYA (B) q (I) with X, Y, Q, Z, R1, n, m, q, A and B as defined above; Hal represents a halogen atom; T represents a hydrogen atom or a group -B (OR ') (OR ") in which - R' and R" represent, independently of one another, a hydrogen atom, an alkyl group, C1-C6, an aryl group selected from the group consisting of benzyl, phenyl, tolyl, xylyl, or - R 'and R "together form a 5- or 6-membered ring optionally substituted with one or more alkyl groups; CI-C4. 8. Use of a compound of formula (I) according to any one of claims 1 to 5, in plastic electronics, in molecular electronics, as a layer for insulating, semiconducting and conductive surfaces. 9. Use of a compound of formula (I) according to any one of claims 1 to 5, for producing organic light-emitting diodes, transparent electrodes, organic photovoltaic cells, organic transistors, single-electron transistors, io sensors and biosensors. 10. Use of a compound of formula (I) according to any one of claims 1 to 5, for producing anticorrosive coatings, surfaces with switchable wetting properties, self-lubricating surfaces, electrochromic coatings, intelligent coatings, adhesion primers. 11. Use of a compound of formula (I) according to any one of claims 1 to 5, in the field of energy storage as electrode materials for batteries, or supercapacities in particular in quality. layers deposited on carbon nanotubes. 12. Material comprising a compound of formula (I) as defined in any one of claims 1 to 5. 13. Article comprising a compound of formula (I) as defined in any one of claims 1 to 5.